Olefin conversion to alicyclic hydrocarbons



United States Patent 3,272,877 OLEFIN CONVERSIONTO ALICYCLIC HYDROCARBONS Raymond A. Franz, Kirkwood, and Richard N. Moore, Creve Coeur, Mo., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed May 16, 1963, Ser. No. 281,008 14 Claims. (Cl. 260666) The present invention relates to a process for the production of alicyclic hydrocarbons. More particularly, the present invention relates to a process whereby alicyclic hydrocarbons are produced by non-catalytic thermal means from olefinic hydrocarbons. Still more particularly, the present invention relates to a process for the production of naphthenic hydrocarbons from olefinic hydrocarbons by non-catalytic thermal means.

The prior literature has proposed the production of naphthenic hydrocarbons from olefin hydrocarbons by purely thermal means. However, the results which are obtained by the prior art processes have been found to be very poor. As will be noted from the examples hereinafter presented, the yields of naphthene hydrocarbons from olefin hydrocarbons by the purely thermal means of the prior art are considerably less than 1% by weight.

It, therefore, is an object of the present invention to provide a new and novel process for the production of alicyclic hydrocarbons. Another object of the present invention is to provide a process for the formation of alicyclic hydrocarbons from olefinic hydrocarbons. Yet another object of the present invention is to provide a non-catalytic process for the conversion of olefin hydrocarbons to alicyclic hydrocarbons. Particularly, it is an object of the present invention to provide a process for the conversion of olefin hydrocarbons to naphthenic hydrocarbons under thermal conversion conditions. Additional objects will become apparent from the following description of the invention herein disclosed.

The process which fulfills these and other objects comprises subjecting olefin hydrocarbons to elevated temperatures and pressures in a non-catalytic reaction zone in the presence of a mixture of at least two different modifying agents. One of the modifying agents is selected from those compounds which under the conditions of the reaction chamber will decompose to or otherwise form hydrogen chloride, hydrogen bromide, hydrogen iodide or combinations thereof. The other modifying agent is either sulfur or a sulfur bearing compound which under the conditions of the reaction chamber will decompose to or otherwise form hydrogen sulfide. This process causes the conversion of olefin hydrocarbons to naphthene hydrocarbons in substantially greater yields than does a similar process carried out in the absence of the mixture of modifying agents.

The term modifying agent used herein, is used merely for simplicity in describing the naphthene formation promoting compounds of the present invention. It merely denotes those compounds which modify the pure thermal non-catalytic process to bring about the formation of naphthenic hydrocarbons in significant yields.

In order to further describe and to illustrate the present invention, the following example is presented. This example is in no way to be construed as limiting the present invention.

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EXAMPLE Four separate runs were made using in each run a propylene feed having a composition of approximately 97% propylene and 3% by weight propane. All four runs were carried out in a sealed stainless steel tube capable of withstanding a pressure of approximately 5,000 p.s.i.g. The inside diameter of the stainless steel tube was approximately 0.18 inches and its capacity was about 4.3 ml. To three of the runs were added modifying agents. In the first run, which shall be designated as run A, elemental sulfur was added in an amount equivalent to 1 mol of sulfur per mols of propylene. To another run, designated as run B, Z-bromopropane was added in the same amount as the sulfur added in the first run. In a third run, designated as run C, both sulfur and 2-bromopropane were added in a mol ratio of 1:1:75, sulfur to bromopropane to propylene. No modifying agent was added to the fourth run which is designated as run D. In all four runs the amount of propylene charged to the reaction tube was approximately 0.85 gm. at approximately 375 C. The duration of all four runs was approximately 30 minutes. Pressure was not measured during any of the runs; however, since they were carried out in a closed container, pressures may be readily calculated from the temperature and quantity of reactants charged to the reaction tube. The re sults of these runs are given in the following table:

The unexpected and outstanding results obtained by using the present invention are readily apparent from the above example. The use of the combination of modifying agents obtained a 260 fold increase in production of methylcyclopentane over the run with no modifying agent and an increase of approximately 325% over the highest yield obtained with a single modifying agent exemplified by run B.

The mixture of at least two different modifying agents useful in the process of the present invention comprises a combination of a modifying agent which under the conditions of the reaction chamber will decompose to or otherwise form hydrogen chloride, hydrogen bromide, hydrogen iodide or combinations thereof with a modifying agent which under the conditions of the reaction chamber will decompose to or otherwise form hydrogen sulfide. The first modifying agent, hereinafter referred to as the halogen-modifying agent, and the second modifying agent, hereinafter referred to as the sulfur-modifying agent, generally are combined in accordance with the present invention in a mol ratio of 1: 100 to 100:1 with 1:5 to 5 :1 being a preferred ratio for combination. The halogen modifying agents are those containing chlorine, bromine or iodine or combinations thereof. Such halogen modifying agents may be either an organic or an inorganic compound. In addition to the halogens, such other elements as carbon, hydrogen, sulfur, oxygen or nitrogen may be present in these modifying agents. If the modifying agent is an organic compound, it may be saturated or unsaturated, aliphatic or aromatic, straight-chained, branched-chain or cyclic in structure. Generally, it may be stated that these halogen modifying agents are those which under the conditions of the reaction chamber will decompose or otherwise form the hydrogen halides HBr, HCl, HI or combinations thereof. This includes not only those compounds of which bromine, chlorine and iodine are a part, but also the halogen gases C1 Br and I Halogen containing modifying agents within the scope of the present invention include the following non-limiting examples.

2-bromopropane 2-chloropropane l-iodopropane l-bromobutane l-chlorobutane 2-iodobutane l-bromopentane 2l-bromopentane 3-chloropentane 2-iodopentane 3-bromohexane 2-bromohexane Z-iodohexane 2-bromo-4-methylhexane 3-chloroheptane 3-bromoheptane bromobenzene chlorobenzene m-dichlorobenzene o-dichlorobenzene p-dichlorobenzene m-dibromobenzene o-dibromobenzene p-dibromobenzene iodobenzene o-iodotoluene m-iodotoluene p-iodotoluene o-chlorotoluene m-chlorotoluene p-chlorotoluene o-b-romotoluene chloroethanoic acid dibromoethanoic acid di-iodoethanoic acid a-chloroacetamide a-bromoacetanilide benzoyl chloride benzoyl bromide benzoyl iodide butanoyl chloride butanoyl bromide butanoyl iodide 2-chloro-1,4-benzenediol 2-bromo-1,4-benzenediol benzene carbonyl bromide Z-iodoheptane 2-bromo-4-ethylhexane 4-bromooctane 3-chlorooctane 2-iodooctane l-bromononane 2-chlorodecane Z-bromodecane 2-bromo-6-methyldecane 3,3-bromomethyldecane 4-iodeundecane l-bromododecane hydrogen chloride hydroen bromide hydrogen iodide m-bromotoluene p-bromotoluene 1,3,5-dibromotoluene o-bromo-chlorobenzene m-bromo-chlorobenzene p bromo-chlorobenzene 2-bromonaphthalene l-chloronaphthalene 1,3-dichloronaphthalene 2-bromo diphenyl 2-chlorodiphenyl 4-chlorodiphenyl chlorine gas bromine gas iodine gas succinyl chloride 4-chloroquinoline ethanoyl iodide hexanoyl chloride decanoyl chloride 2-bromoethanol 2-chloroethanol bis-B-chloroethylether chloromethoxy methane cyclohexylchloride cyclohexylbromide carbon tetrachloride 2-chloro-3-hexene 2-bromo-2-pentene 1-chloro-4-nitronaphthalene Im0-4-0ctene benzene carbonyl chloride The halogen containing modifying agents most useful in the practice of the present invention are those which contain a halogen from the group consisting of bromine, chlorine and iodine and the elements carbon and/or hydrogen. These compounds are the halogen substituted hydrocarbons and hydrogen halides. There is no critical limit to the molecular weight of the modifying compound other than one of practicality in handling. It will generally be somewhat preferred, from a purely practical ,4 standpoint, to use those compounds which are normally liquid or normally gaseous. In the practice of the present invention, the preferred compounds are the monoand di-halogen substituted hydrocarbons of no more than 8 carbon atoms and the hydrogen halides. Though all of the halogens from the group consisting of bromine, chlorine and iodine are operable in the present invention, it is generally prefer-red to use those compounds containing chlorine and bromine with bromine being preferred over chlorine.

The sulfur modifying agents useful in the present invention may be either organic or inorganic compounds as well as elemental sulfur. They may be of virtually any molecular Weight, being limited only by practicality, practical in this sense referring to ease of handling in the process. If organic compounds, the modifying agents may be straight-chain, branched-chain, or cyclic, aromatic or non-aromatic, saturated or unsaturated. When elemental sulfur is the modifying agent, either of its forms may be used. Generally, the requirement of the sulfur modifying agent may be stated as any compound which, when placed in the reaction chamber under the conditions of temperature and pressure of the reaction, will decompose to or otherwise form hydrogen sulfide. Among the sulfur-bearing compounds useful in the present invention are the following non-limiting examples:

allyl sulfiide methyl-benzenesulfonic acid benzyl sulfide butyl sulfate 2-methyl-2-butanethiol dithio-carbamic acid butylsulfide thiol-carbamic acid dithiol-carbonic acid 1,2-ethanedisulfonic acid ethyl sulfone methanethiol 2-bromothiophene 2,5-diiodothiophene l-decanol sulfate methyl sulfone bis-(p-dichloroethy-l) sulfide ethylene sulfide furfuryl mercaptan isoamyl disulfide methyl disulfide l-naphthalenethiol l-propanethiol 2,2-thiodiethanol benzenesulfonic acid p-chloro-benzenesulfonic acid benzyl sulfoxide thionaphthene butyl sulfone 3-methylthiophene benzoyl disulfide elemental sulfur 2-methyl-1-butanethio1 thiono-carbamic acid tert-octanethiol cetyl sulfate 1,2-ethanedithiol ethionic anhydride ethyl disulfide ethyl sulfoxide l-heptanethiol methyl sulfoxide isoamyl sulfide 2-chlorothiophene methyl sulfide 1 2,3-dimethylthiophene l-pentanethiol methyl sulfate 2-methyl-1-propanethiol octyl sulfate thiophene ethyl methyl sulfide o-bromo-benzensulfonic thionaphthenequinone acid o-formyl-benezenesulfonic a-toluenethiol acid thiophenol trithio-carbonic acid dodecyl sulfate ethyl sulfite ethyl sulfuric acid 2,2-bithiophene butyl sulfoxide benzyl disulfide S-methyI-I-butanethiol As noted from the above list of compounds, the sulfur bearing modifying agents may contain such elements,

other than sulfur, as carbon, hydrogen, oxygen, nitrogen, chlorine, bromine, iodine, and the like. Among the most useful modifying agents are elemental sulfur and such sulfur bearing compounds as mercaptans or thiols both aliphatic and aromatic, hydrogen sulfide and thio ethers. Also within this list of preferred compounds are those derived from dissolving sulfur in tertiary amines at elevated temperatures. The preferred sulfur modifying agents are elemental sulfur and sulfur bearing compounds containing the additional elements of carbon and/or hydrogen. When using sulfur bearing compounds containing carbon and hydrogen, it is generally preferred that they contain no greater than 20 carbon atoms. A particularly preferred group of sulfur modifying agents are the thiophenols, elemental sulfur, hydrogen sulfide and mercaptans of 1 to carbon atoms.

The present invention contemplates the use of a mixture of a halogen-modifying agent and a sulfur-modifying agent. While generally, this mixture requires two separate modifying compounds, it is within the scope of the present invention that both modifying agents may be supplied by a single compound. For example, certain compounds such as Bfi-dichloroethyl sulfide contains both halogen and sulfur constituents and on being subjected to the conditions of the reaction zone will supply both a hydrogen halide and hydrogen sulfide to the reaction zone. Thus, those compounds which on being subjected to the conditions of the reaction chamber will decompose to or other- Wise form both the halogen modifying agent and the sulfur modifying agent may be used instead of two separate compounds, one of which supplies the halogen and the other of which supplies the sulfur.

The amount of the mixture of modifying agents generally used is within the range of 0.01 to 10 mol percent of the total feed. It is preferred, however, that the amount of modifying agent be within the range of 1 to 4 mol percent of the total feed.

Virtually any olefin hydrocarbon may be converted to alicyclic hydrocarbons according to the process of the present invention. Generally such olefins will contain from 2 to 20 carbon atoms. As used herein, the term olefin is meant to include not only mono-olefin hydrocarbons, but diolefins as well. Further, acetylenic hydrocarbons may be converted to alicyclic hydrocarbons by the process of the present invention. The preferred use of the present invention is in the conversion of monoolefin hydrocarbons of 2 to 10 carbon atoms to alicyclic hydrocarbons. Non-limiting examples of such monoolefin hydrocarbons are ethenes, propenes, butenes, pentenes, hexenes, heptenes, octenes, nonenes, decenes, iso-butenes, iso-pentenes, iso-hexenes, iso-heptenes, isooctenes, iso-nonenes, and iso-decenes. The olefin hydrocarbon feed to the present invention need not be a pure olefin feed stream but will generally contain no less than 50 mol percent olefin hydrocarbon. This limitation is primarily one of commercial practicality, however, rather than operability. Impurities which may be tolerated in the feed to the present process may include saturated hydrocarbons such as nand iso-paraffins and the like.

The hydrocarbon conversion process disclosed herein is ordinarily carried out at elevated temperatures within the range of 250 C. to the cracking temperature of the particular olefin hydrocarbons in the feed. The preferred temperatures for operating the present invention are, however, within the range of from about 300 to 500 C. For treating the preferred feeds of the present invention, temperatures of 325 to 475 C. will generally provide the optimum in yield of alicyclic hydrocarbon product.

The process disclosed herein is operated at elevated pressures, usually at a pressure greater than 200 p.s.i.g. The upper limit for pressures in carrying out the present invention is limited only by the strength of the reaction vessel. Such pressures will seldom exceed 20,000 p.s.i.g. Generally, it may be stated that the higher the pressure the better the results of the hydrocarbon conversion reaction. The preferred pressures for operating the present process will be above 1000 p.s.i.g. and, most often, below 20,000 p.s.i.g. The optimum pressures for carrying out the present invention may be generally stated as the minimum pressure which may be obtained by the partial pressures of the reactants within a closed reaction zone at the particular temperature at which the reaction is be ing carried out.

The present hydrocarbon conversion process may be operated as either a batch or a continuous process. The equipment necessary for either type of operation may be any conventional equipment which will withstand the relatively high pressures involved in the present process.

The residence time of the reactants within the reaction zone generally ranges from 0.001 to 240 minutes. However, it is preferred that the residence time range from no less than 0.05 minutes to no greater than 120 minutes.

The apparatus which may be used in carrying out the present invention may be of virtually any design. Of course, it will be of such design and materials of construction as to withstand the relatively high pressures and temperatures of the present process. Its primary requirement is only that it be consistent with good engineering principles.

What is claimed is:

1. A process for producing alicyclic hydrocarbons from olefin hydrocarbons which comprises subjecting olefin hydrocarbons of 2 to 20 carbon atoms in the absence of a catalyst to a temperature of 300 to 500 C. and a pressure of 200 to 20,000 p.s.i.g. in a non-catalytic reaction zone in the presence of a mixture of at least two different modifying agents, one of said modifying agents being selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide and mixtures thereof and compounds and elements which under the conditions of the reaction zone will form a member of the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide and mixtures thereof, and the other of said modifying agents being one selected from the group consisting of hydrogen sulfide, elemental sulfur and compounds which under the conditions of the reaction zone will form hydrogen sulfide.

2. The process of claim 1 wherein the total amount of the mixture of at least two different modifying agents is from 0.01 to 10 mole percent of the total feed.

3. The process of claim 1 wherein the total amount of the mixture of at least two different modifying agents is from 1 to 4 mole percent of the total feed.

4. The process of claim 1 wherein the temperature is 300 to 500 C.

5. The process of claim 1 wherein the mol ratio between the halogen modifying agent and the sulfur modifying agent is 1:100 to :1.

6. The process of claim 1 wherein the halogen modifying agent is a halogen substituted hydrocarbon of no greater than 6 carbon atoms in which the halogen is one selected from the group consisting of iodine, bromine and chlorine.

7. The process of claim 1 wherein the halogen modifying agent is a di-halogen substituted hydrocarbon of no greater than 6 carbon atoms in which the halogens are selected from the group consisting of iodine, bromine, chlorine and combinations thereof.

8. The process of claim 1 wherein the halogen modifying agent is selected from the group consisting of HCl, HBr and HI.

9. The process of claim 1 wherein the halogen modifying agent is selected from the group consisting of iodine, bromine and chlorine gases.

10. The process of claim 1 wherein the sulfur modifying agent is elemental sulfur.

11. The process of claim 1 wherein the sulfur moditying agent is a sulfur bearing compound selected from the group consisting of mercaptans, hydrogen sulfide, thio ethers and sulfur dissolved in tertiary amines.

12. The process of claim 1 wherein the olefin hydrocarbons are mono-olefin hydrocarbons of 2 to 10 carbon atoms.

13. The process of claim 1 wherein the temperature is 325 to 475 C.

14. The process of claim 1 wherein the mol ratio between the halogen modifying agent and the sulfur modifying agent is 1:5 to 5:1.

References Cited by the Examiner UNITED STATES PATENTS Gaylor et al 260-666 Amos et al 260-680 Foster 260-666 Ballard 260-666 Guest 260-666 

1. A PROCESS FOR PRODUCING ALICYCLIC HYDROCARBONS FROM OLEFIN HYDROCARBONS WHICH COMPRISES SUBJECTING OLEFIN HYDROCARBONS OF 2 TO 20 CARBON ATOMS IN THE ABSENCE OF A CATALYST TO A TEMPERATURE OF 300 TO 500*C. AND A PRESSURE OF 200 TO 20,000 P.S.I.G. IN A NON-CATALYTIC REACTION ZONE IN THE PRESENCE OF A MIXTURE OF AT LEAST TWO DIFFERENT MODIFYING AGENTS, ONE OF SAID MODIFYING AGENTS BEING SELECTED FROM THE GROUP CONSISTING OF HYDROGEN CHLORIDE, HYDROGEN BROMIDE, HYDROGEN IODIDE AND MIXTURES THEREOF AND COMPOUNDS AND ELEMENTS WHICH UNDER THE CONDITIONS OF THE REACTION ZONE WILL FORM A MEMBER OF THE GROUP CONSISTING OF HYDROGEN CHLORIDE, HYDROGEN BROMIDE, HYDROGEN IODIDE AND MIXTURES THEREOF, AND THE OTHER OF SAID MODIFYING AGENTS BEING ONE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN SULFIDE, ELEMENTAL SULFUR AND COMPOUNDS WHICH UNDER CONDITIONS OF THE REACTION ZONE WILL FORM HYDROGEN SULFIDE. 